Differential-dyeing textiles

ABSTRACT

TEXTILES OF AT LEAST TWO DIFFERENT POLYAMIDE YARNS WHEREIN FROM 10 TO 90% BY WEIGHT OF THE YARN IN THE TEXTILE IS YARN OF A POLYAMIDE WHICH CONTAINS FROM 1 TO 15% BY WEIGHT OF XYALKYLATED POLYAMIDE. THESE TEXTILES ARE DYED IN CONTRASTING SHADES IN A SINGLE-BATH PIECEDYEING PROCEDURE.

United States Patent US. Cl. 821 B 8 Claims ABSTRACT OF THE DISCLOSURETextiles of at least two different polyamide yarns wherein from to 90%by weight of the yarn in the textile is yarn of a polyamide whichcontains from 1 to by weight of oxyalkylated polyamide. These textilesare dyed in contrasting shades in a single-bath piecedyeing procedure.

The invention relates to differential-dyeing textiles comprising atleast two different polyamide yarns.

It is known that yarn which have been dyed different colors may beprocessed into multicolored textiles. In order to obtain a certain rangeof multicolored textiles it is necessary to keep a large inventory ofdyed yarns.

It is an object of this invention to provide differentialdyeing textilesof polyamide yarns which can be dyed in piece form. This and otherobjects which will appear hereinafter are achieved by the invention.

In accordance with this invention, textiles of at least two differentyarns of filament-forming synthetic linear polyamides comprises from 10to 90% by weight of yarn (A) of a polyamide which contains from 1 to 15%by weight of oxyalkylated polyamide.

Polyamides for the purposes of this invention are synthetic linearpolyamides having recurring amide groups in the main chain.

The presence of yarn (A) of polyamide containing 1 to 15%, preferably 3to 8%, by weight of oxyalkylated polyamide in the textiles is essentialaccording to this invention. The production of polyamides modified withoxyalkylated polyamides may be carried out by conventional incorporationof the oxyalkylated polyamide, for example by fine distribution bykneading and homogenizing the melt, into filament-forming syntheticlinear polyamides. Examples of such polyamides are polycondensates oflactams such as e-caprolactam, capryllactam, laurolactam or mixtures ofthese lactams, and the polycondensates of salts of diamines anddicarboxylic acids such as the salts of adipic acid. suberic acid orsebacic acid and hexamethylenediamine, octamethylenediamine ordodecamethylenediamine or cocondensates of the said polyamide-formingstarting materials. It is possible to add the said oxyalkylatedpolyamide to the polyamide-forming starting materials prior to or duringthe production of the said polycondensates. Particularly favorableresults are achieved when the modifying agent which is present in thefilament-forming polyamide in a separate phase has a particle size of0.01 to 0.5 micron.

The oxyalkylated polyamides may be prepared by known methods, forexample according to Belgian Pat. No. 665,018 by reaction of a1,2-alkylene oxide such as ethylene oxide and/or 1,2-propylene oxidewith a polyamide under superatmospheric pressure at elevatedtemperature, particularly at temperatures of from 60 to 100 C. Thereaction may be carried out in the absence or presence of organicsolvents and/or reducing or oxidiz- 3,707,344 Patented Dec. 26, 1972 iceing agents, the alkylene oxides preferably being reacted with thepolyamides in the ratio by weight of 0.5:1 to 4:1.

Suitable polyamides from which the oxyalkylated polyamides (used asantistatic agents) may be prepared are for example polycondensatesproduced by conventional methods from lactams such as caprolactarn,capryllactam, laurolacta'm or mixtures of these lactams; salts of thetype diamine/dicarboxylic acid, such as the salts of adipic acid,suberic acid or sebacic acid and hexamethylenediamine,octamethylenediamine or dodeca-methylenediamine, or copolyamides of thesaid polyamide-forming starting materials. Polyamides which have a lowcrystallinity such as copolyamides or polyamides which have beenobtained by quenching the polymer melt, for example of moltenpolycaprolactam, are generally particularly suitable.

Yarns (B) which may be present in the textiles in addition to the yarnwhich is essential according to the invention are for example yarns ofunmodified filament-forming synthetic linear polyamides such as thepolycondensates of lactams such as e-caprolactam, capryllactam,laurolactam or mixtures of these lactams and the polycondensates ofsalts of diamines and dicarboxylic acids such as the salts of adipicacid, suberic acid or sebacic acid and hexamethylenediamine,octamethylenediamine or dodecamethylenedia-mine or cocondensates of thesaid polyamide-forming starting materials. Filament-formingpolycaprolactam and polyhexamethylene adiparnide are particularlysuitable as the unmodified polyamides. Products having a relativeviscosity of from 2.2 to 2.8 have proved to be favorable.

Other yarns (C) which may be present in the textiles in addition to theyarn which is essential in accordance with the invention are those ofconventional filamentforming synthetic linear polyamides having from 50to- 130, particularly from 60 to 110, milliequivalents per kilogram ofbasic groups. The production of these polyamides may be carried out forexample by using additional monofunctional or bifunctional primaryamines such as hexamethylenediamine, in the production of the polyamidesfrom the abovementioned lactams or dicarboxylic acid/diamine salts. Itis also possible to introduce tertiary amine groups into the polyamidesby using polyamide units bearing tertiary amine groups in the productionof polyamides from the said lactams or dicarboxylic acid/diamine salts.It is also possible to activate basic groups for dyeing by using in theproduction of the polyamides in the said manner 0.01 to 0.3% by weightwith reference to polyamide of phosphorus in the form of oxyacids ofphosphorus or their esters.

Other yarns (D) which may be present in the textiles in addition to theyarn which is essential in accordance with this invention are those ofpolyamides which can be dyed full shades with basic dyes. Polyamideswhich contain from 50 to milliequivalents per kilogram of sulfonategroups in the form of alkali metal salts are suitable for the productionof these yarns. Production of these polyamides may be carried out forexample by using aliphatic, cyeloaliphatic or aromatic polyamide unitsbearing sulfonate groups in appropriate amounts in the production of thepolyamides from the said lactams or dicarboxylic acid/diamine salts. Forexample the sodium or potassium salt of 5-sulfoisophthalic acid issuitable for the incorporation.

Textiles having the following yarn combinations are preferred:

(1) yarn (A) with yarn (B) (2) yarn (A) with yarn (C) (3) yarn (A) withyarn (D) or (4) yarn (A) with yarn (B) and with yarn (D).

The polyamide yarns which are essential according to the invention andthe polyamide yarns used with them may contain conventional additivessuch as stabilizers or delustrants such as titanium dioxide. They may beprocessed smooth or textured into textiles. Examples of suitabletexturing methods are gear crimping, stuffing box crimping or falsetwisting and air-texturing. The yarns may be composed of continuousfilaments or staple fibers. Yarns and filament bundles are equivalent.

The term textiles in this specification includes hosiery, knitwear,woven and nonwoven goods and particularly carpets.

The amount of the yarn (A) which is essential according to the inventionand consists of polyamides having a content of oxyalkylated polyamidesis to 90%, advantageously 20 to 80%, by weight and consequently theproportion of other polyamide yarns in the textiles is 90 to 10% and 80to 20% by weight respectively. The ratio of the yarns to one another mayvary within these limits. The textiles may contain one or more than onekind of yarn in addition to the yarn which is essential according to theinvention. The ratio of the yarns present in the textiles in addition tothe essential yarn may in turn vary Within wide limits. The yarncombination chosen is dictated by the desired color pattern and coloreffects in the textile. For a strong optical effect it may beadvantageous for the various yarns to be present in about equal amounts,i.e. in a combination of two yarns the amount of each may be from 40 to60% by weight and in a triple combination each may be present in anamount of 20 to 40% by weight, while in a combination of four yarns theamount of each may be from to 30% by weight. The distribution of colorin the yarn blends in relation to the dyes to be used may easily beascertained by simple preliminary experiments. The distribution of yarnsin the textile may be varied markedly in weaving or tufting so that thezones of different coloration may be varied substantially.

The textiles are preferably piece-dyed. Generally it is advantageous tocarry out the dyeing from an aqueous liquor by the one-bath method. Whena tone-on-tone effect or a moulin dyeing having contrasting shadesaccording to the content of different yarns is desired, acid dyes shouldbe used exclusively. The pH has a certain influence on the degree ofcontrast, the contrast usually being better the higher the pH is. A pHof 4 to 9, particularly 7 to 9, has proved to be very favorable. Whencomplementary colorations are to be obtained, it is advantageous to usedisperse dyes in addition to the acid dyes.

For cross dyeing it is necessary for the textiles to contain yarns ofbasic-dyeable polyamides. Dyeing is carried out with acid dyes and basicdyes and if necessary with disperse dyes all at the same time to achievecross dyeing. A pH of the dye liquor of 4 to 8, particularly 6 to 8, hasproved to be favorable in this case.

In dyeing textiles in the presence of disperse dyes it is advantageousfor the yarns from different polyamides to have the same affinity forthe disperse dyes.

Conventional dyes are suitable. For example dyes of the anthraquinone orazo series having sulfonic groups are suitable as acid dyes. Acid dyesgive a higher degree of contrast the higher the number of sulfonicgroups present in the molecule. Thus three sulfonic groups produce amore marked contrast than two sulfonic groups or one sulfonic group.Examples of basic dyes are those having basic tertiary or quaternarynitrogenous groups.

Piece dyeing may be carried out batchwise or continuously, for exampleby drawing a length of carpet through the dye-bath. The one-bath methodof piece dyeing differential-dyeing textiles according to the inventiontoneon-tone or multicolor effects constitutes an extremely efficient andeconomical procedure. The inventory is minimized. Moreover a variety ofcolor styling patterns can be prepared because a great many variationsare possible in the composition of the yarns, in the arrangement ofthese yarns in the textiles and in the choice of dyes.

Textiles according to this invention also have the valuable property ofa decreased static electrification, particularly with an increasingcontent of the yarns which are essential according to the invention.

The following examples illustrate the invention. The parts andpercentages specified in the examples are by weight.

EXAMPLE 1 (a) Production of an oxyalkylated polyamide: Ethylene oxide isforced onto 160 parts of powdered polycaprolactam (K value 66, internalviscosity determined according to the formula of H. Fikentscher,Cellulosechemie, 13, 58 (1932), so that a pressure of 5 to 10atmospheres gauge prevails in the gas space and up to 560 parts ofethylene oxide react. The reaction temperature is to C. The reactor isvented and purged with nitrogen. 720 parts of oxyalkylated polyamide isobtained which has a K value (measured as a 1% solution in concentratedsulfuric acid) of 42.

(b) Dyeing yarn blends: To detect the differential dye takeup, 10 partsof yarn of polycaprolactam having a K value of 72 (total denier, 1200;67 individual filaments) together with 10 parts of polycaprolactam yarnof the same denier and number of filaments to which during thepolycondensation 7.5% of the oxyethylated polyamide prepared accordingto Example 1(a) has been added are dyed a liquor as follows:

In an aqueous dye liquor which contains 0.25% of the acid dye AcilanFast Navy Blue R (with reference to the total weight of yarn) and 0.5part per liter of an oxyalkylated emulsifying agent and which has beenbuffered to pH 7.2 with 0.3 part per liter of boric acid and 0.01 partper liter of borax, the yarn blend is dyed at the boil for one hour at aliquor ratio of 50:1 until the liquor is exhausted. The dye pickup ofthe two yarns is determined by extraction of the separated yarns with a1:1 mixture of pyridine and water in a Soxhlet apparatus. The followingpercentage distribution of the dye in the yarns is obtained:

Yarn: Amount of dye taken up, percent Polycaprolactam 21.9 Modifiedolycaprolactam 78.1

The better dye absorption of the polyamide which has been modified withoxyalkylated polyamide may be clearly seen.

EXAMPLE 2 In accordance with Example 1(b), the yarn is dyed in a dyeliquor at a liquor ratio of 50:1 which contains 0.5% of the acid dyeSupranol Yellow 0 with reference to the Weight of yarn in all, and 0.5part per liter of a conventional oxyalkylated emulsifier and which hasbeen buffered to pH 8.0 with 0.4 part per liter of boric acid and 0.19part per liter of borax. The following dye distribution is obtained:

Yarn: Amount of dye taken up, percent Polycaprolactam 31.4 Modifiedpolylactam 68.6

EXAMPLE 3 A combination of equal parts of yarns of (I) polycaprolactamhaving a K value of 73;

(II) olycaprolactam having a K value of 74 which has 61 milliequivalentsof basic groups per kilogram; and

(III) olycaprolactam having a K value of 67 which has been modified by7.5% of the oxyethylated polyamide, prepared in Example 1(a) is dyedaccording to the conditions of 1(b) or 2. The following percentage dyedistribution is found:

Acilan fast Supranol Yam navy blue R yellow I 4. 8 8. 1 II 64. 9 74. 4III 30. 3 17.

The midposition of yarn III modified with the oxyalkylated polyamideaccording to the invention may be clearly seen,

EXAMPLE 4 A combination of equal parts of yarns of:

(I) polyhexamethylene adipamide having a K value of (II)polyhexamethylene adipamide having a K value of 70.4 which has 79milliequivalents of basic groups per kilogram; and

(III) polycaprolactam having a K value of 67 which has been modifiedwith 7.5% of the oxyethylated polyamide prepared in Example 1(a) is dyedunder the conditions according to Example 1(b) or 2. The followingpercentage dye distribution are found:

Acilan fast Supranol Yarn navy blue R yellow 0 EXAMPLE 5 EXAMPLE 6 Thetwo yarns specified in Example 1(b) are textured by the stuffing boxmethod and twisted at the rate of 50 turns per meter. By tufting thismaterial on a jute twill material, a piece of carpet is prepared whichcontains 550 g./m. of pile material. A sample piece of this carpet isdyed on the beck at pH 8 with 0.3% of Brilliant Alizarin Milling BlueFGL and 0.9% of Celliton Yellow 4 GE (with reference to the piece ofcarpet) at a liquor ratio of 80: 1. The sample exhibits a yellowishgreen moulin pattern after dyeing.

EXAMPLE 7 A knitted article is made up from equal parts of yarn of:

(I) polycaprolactam having a K value of 69 which has been modified with5% by weight of the oxyalkylated polyamide prepared in Example 1(a); and

(II) polyhexamethylene adipamide having a K value of 71 which contains1.5% by weight of sodium S-sulfoisophthalate and 0.4% by weight ofhexamethylene diamine condensed therein.

The yarn has a denier of 1100 with 67 individual filaments. When thearticle is dyed in an aqueous dyebath having a pH of 7.1 which contains0.5 by weight of the acid dye Acilan Fast Navy Blue R and 0.5% by weightof the basic dye Basacryl Yellow 7 GL (each with reference to thearticle) a pattern is obtained at a liquor ratio of 50:1 in which yarn(I) is dyed pure blue and yarn (II) is dyed pure yellow. Thus a crossdyeing having clearly separated color areas is obtained according tothis example.

EXAMPLE 8 (I) A rnixture of 100 parts of olycaprolactam chips having a Kvalue of 73 is melted and homogenized with 5 parts of the oxyalkylatedpolyamide chips prepared according to Example 1(a) in a twin shaftextruder.

(II) Polycaprolactam chips having a K value of 73 which contain 78milliequivalents per kilogram of basic terminal groups are prepared bypolycondensation of caprolactam with 0.3% by weight of hexamethylenediamine as regulator followed by annealing for twenty-four hours of theextracted chips at 160 C. in a stream of nitrogen.

Yarns having a drawn denier of 1100/67 are spun from both portions,textured by the edge drawing method and twisted at the rate of 50 turnsper meter. By tufting this yarn on a jute twill material a piece ofcarpet is prepared having 600 g./m. of pile material. When this sampleis dyed on the beck with 0.7% of Lanasyn Pure Red R with reference tothe weight of the sample at a pH of 7.2 and a liquor ratio of 80:1, apale red/dark red moulin pattern is obtained in which the paler fibersare those prepared according to (I) and the darker fibers are thoseprepared according to (II).

EXAMPLE 9 Three yarns having a drawn denier of 40/10 are spun from thefollowing polyamides:

(I) a polyamide prepared according to Example 3(1);

(II) a polyamide prepared according to Example 8(I);

and

(III) a polyamide prepared according to Example 7(II).

Using these yarns in the ratio 1:1:1, stockings are knitted in shepherdscheck pattern. When these stockings are dyed with 1.5 of Lanapearl Red Band 0.5 of Sevron Blue B, with reference to the weight of the article,at a pH of 6.5 and a liquor ratio of 50:1, a blue/pale red/dark redshepherds check pattern is formed, yarn from (I) being pale red, yarnfrom (II) dark red and yarn from (III) blue.

We claim:

1. A difierential-dyeing textile which can be dyed in piece form andwhich is composed of at least two diiferent yarns of filament-formingsynthetic linear polyamide having amide groups recurring in the mainchain wherein from 10 to by weight of the yarns is a yarn A of apolyamide which contains from 3 to 8% by weight of an oxyalkylatedpolyamide which has been obtained by oxyalkylation with ethylene oxideor 1,2-propylene oxide in a ratio by weight of alkylene oxide: polyamideof about 0.5:1 to 4:1.

2. A differential-dyeing textile as claimed in claim 1 which comprisesfrom 10 to 90% by weight of said yarn (A) and 90 to 10% by weight of atleast one member of the group consisting of yarn (B) of unmodifiedpolyamide and of yarn (C) of a polyamide having from 50 tomilliequivalents per kilogram of basic groups and of yarn (D) of apolyamide having 50 to milliequivalents per kilogram of sulfonategroups.

3. A differential-dyeing textile as claimed in claim 1 which comprisesfrom 10 to 90% by weight of said yarn (A) and 90 to 10% by weight of ayarn (B) of an unmodified polyamide.

4. A differential-dyeing textile as claimed in claim 1 which comprises10 to 90% by weight of said yarn (A) and 90 to 10% by weight of a yarn(C) of a polyamide with 50 to 130 millequivalents of basic groups.

5. A differential-dyeing textile as claimed in claim 1 which comprises10 to 90% by weight of said yarn (A) 7 and 90 to 10% by weight of a yarn(D) of a polyamide having to 150 milliequivalents per kilogram ofsulfonate groups.

6. A differential-dyeing textile as claimed in claim 1 which comprises10 to by weight of said yarn (A) and 90 to 10% by weight of yarn (C) ofa polyamide having 50 to milliequivalents per kilogram of basic groupsand of yarn (D) of a polyamide having 50 to milliequivalents perkilogram of sulfonate groups.

7. A textile as claimed in claim 1 which has been piecedyed in a singlebath to provide a contrasting coloration.

8. A textile as claimed in claim 7 wherein at least one acid dye hasbeen applied to the textile from a single bath.

References Cited UNITED STATES PATENTS 10 ROBERT F. BURNETT, PrimaryExaminer L. T. KENDELL, Assistant Examiner US. Cl. X.R.

